1, 4-naphthoquinone compounds and material colored therewith



Patented Mai. 10, 1942 S TAT E S PAT E @FFEQE lA-NAPHTHOQUINONE COMPOUNDS AND MATERIAL COLORED THEREWITH Joseph B. Dickey and James ter, N. Y., assignors to pany, Rochester, N. Y.,

Jersey G. McNally, Roches- Eastman Kodak Coma corporation of New 7 Claims.

This invention relates to the art of dyeing or coloring. More particularly it relates to furan amino 1,4-naphthoquinone compounds and the application of the nuclear unsulfonated compounds for the coloration of organic derivatives of cellulose, especially cellulose acetate silk by dyeing, printing, stenciling or like methods.

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed cellulose organic acid esters such as cellulose acetate, cellulose formate, cellulose propionate or cellulose butyrate and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose such as cellulose acetate-propionate, cellulose acetate-butyrate and the cellulose ethers such as methyl cellulose, ethyl cellulose or benzyl cellulose. While our invention Will be illustrated more particularly in connection With the coloration of cellulose acetate, a material to which the invention is especially adapted, it will be understood that it applies to the coloration of other organic derivatives of cellulose such as those just mentioned.

It is an object of our invention to provide a new class of lA-naphthoquinone dye compounds. Another object of our invention is to provide a process for the coloration of organic derivatives of cellulose. A further object is to provide colored organic derivative of cellulose textile materials which are of good fastness to light and washing. A still further object is to provide a satisfactory process for the preparation of the new lA-naphthoquinone dye compounds of our invention.

The lA-naphthoquinone compounds of our invention by means of which the above objects are accomplished or made possible are characterized in that they contain a furan amino group. These compounds have, for the most part, the probable general formula:

2 o t 1T): 6 33 t t wherein X represents a furan amino radical and Y and Z each represents a member selected from the group consisting of a hydroxy group, a

furan-, an alkyl-, a cycloalky1-, an allyl-, an aralkyl-, an aryland a heterocyclic-amino group. The lA-naphthoquinone compounds of our invention can contain substituents in addition to the amino substituents mentioned. Illustrative of such substituents may be mentioned alkyl, alkoXy and halogen.

The substituted 1,4-naphthoquinone compounds of our invention can be prepared by re acting 5,8-dihydroxy-lA-naphthoquinone, leuco 5,8-dihydroxy-1,4-naphthoquinone or a mixture of 5,8-dihydroxy-1,4-naphthoquinone and leuco 5,8-dihydroxy-lA-naphthoquimne with a furan amine. In those cases Where the 1,4-naphth-oquinone nucleus contains both the residue of a furan amine and another amine such as an alkylamine, a cycloalkyl amine, allylamine, an arylamine, an aralkylamine and a heterocyclic amine, the reaction may be carried out using a mixture of a furan amine and one or more of the amines just mentioned, or stepwise. Where this latter procedure is employed the 5,8-dihydroxy-1,4-naphthoquinone compound may first be caused to react with a furan amine and then with the desired amine, or with an amine, other than a furanamine, and then with the desired furan amine. The reaction may be carried out in an inert solvent or diluent medium such as methanol, ethanol, butanol, carbitol, water, pyridine and dimethylaniline. Substituents such as halogen, alkyl and alkoxy can be introduced into the. lA-naphthoquinone nucleus by methods known for the introduction of such groups.

While our invention relates broadly to substituted IA-naphthoquinone compounds containing a furan amino group, it relates more particularly to substituted 1,4-naphthoquinone compounds in which the furan amino group is selected from the group consisting of those having the general formulae:

wherein B represents hydrogen, -(CH2)$OH or -(CH2)NH2, wherein :2: represents a whole number above zero, and n is a small whole number above zero.

Examples of furan amines employed in the process of our invention include Furfurylamine HCCH H H HO o-cmrvm ,B-furylethylamine and 8-tetrahydrofurylethylamine for example, likewis may be employed in the process of our invention.

The term alkyl as used herein and in the claims, unless otherwise indicated, includes not only unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group or a butyl group but also substituted alkyl groups such as fi-hydroxyethyl, ,B-hydroxypropyl, fin-hydroxypropyl, 'y-hydroxypropyl, A-hydroxybutyl, methoxyethyl, ,B-ethoxyethyl, fiV-methoxy-fiethoxyethyl, fl-chloroethyl, 'y-chloropropyl, flsulfoethyl, 'y-sulfopropyl, fi-sulfatoethyl,

CH2CH2NH2 CH2CH2N-C2H5 for example.

Illustrative cycloalkylamines include cyclohexylamine and cyclobutylamine. Illustrative arylamines include, for example, aniline, a-naphthylamine, o-m-p-anisidine, o-m-p-toluidine, o-m-p-phenylene diamine, o-m-p-phenetidine, l-amino-B-naphthol and. o-m-p-aminophenol. Similarly, illustrative aralkylamines include benzylamine and phenylethylamine. Heterocyclic amines which can be employed include; for example, aminopyridines, aminoquinolines, aminocarbazoles, aminoacridines and aminoacridones.

The nuclear unsulfonated compounds of our invention can be employed for the dyeing or coloration of organic derivatives of cellulose. The nuclear sulfonated compounds possess little or no utility for the dyeing of organic derivatives of cellulose but can be employed for the dyeing of Wool and silk. Sulfonated compounds when desired can be prepared by sulfonation of the twenty hours.

unsulfonated compounds in known fashion. Alternately the sulfonic group can be initially present in the 5,8-dihydroxy-lA-naphthoquinone nucleus.

The following examples illustrate the preparation of the l/l-naphthoquinone compounds of our invention.

Example 1.

19 grams of 5,8-dihydroxy-1,4-naphthoqui11one, grams of a 40% aqueous solution of tetrahydrofurfurylamine and 1 gram of zinc dust are heated in a shaking autoclave at 50 C. for The crystalline reaction product resulting is recovered by filtration and washed with water. If desired, it can be purified by crystallization from a solvent such as acetic acid. The reaction product has the probable formula:

and colors cellulose acetate silk bluish-green shades.

Furfurylamine, B-furylethylamine and 5-w-hydroxy-Z-tetrahydrofurfurylamine, for example, can be substituted for the tetrahydrofurfurylamine of the example to obtain corresponding dye compounds which are included within the scope of our invention.

Example 2 19 grams of 5,8-dihydroxy-1,4-naphthoquinone, 160 grams of a 30% aqueous solution composed of equal molecular parts of v-tetrahydrofurfurylpropylamine and tetrahydrofurfurylamine and 3 grams of boric acid'are heated together in a shaking autoclave at 50C. for 20 hours. The reaction product is worked up as described in Example 1 and has the probable formula:

The product obtained by the foregoing reaction dyes cellulose acetate silk a bluish-red shade.

Example 3 are reacted together and the reaction product is worked up as described in Example 1. The dye product obtained dyes cellulose acetate silk a bluish-green shade.

Example 4 19 grams of 6-methyl-5,8-dihydroxy-1,4-naphthoquinone, 160 grams of a 40% aqueous solution composed of equal molecular parts of tetrahydrofurfurylamine, methylamine and ethylamine and 1 gram of zinc dust are heated in an autoclave at 50-60 C. for 15 to 20 hours with agitation. The reaction product is worked up as described in Example 1 and has the probable formula:

This dye product colors cellulose acetate silk a bluish-green shade.

Example 5 6 grams of leuco naphthazarine, 13 grams of 5,8-dihydroxy-1,4-naphthoquinone, 160 grams of a 40% aqueous solution composed of equal molecular parts of B-tetrahydrofurfurylamine, methylamine and ethanolamine are heated in an autoclave at 5070 C. for 15 to hours with agitation. The reaction product is worked up as described in Example 1. It dyes cellulose acetate silk a bluish-green shade.

The above reaction may be carried out, for example, using ethylamine, propylamine, isopropylamine or butylamin in place of methylamine and propanolamine (1,2 and 1,3), butanolamine (1,2; 1,3 and 1,4) and glycerylamine, for example, in place of ethanolamine. The reaction products thus obtained color cellulose acetate silk bluish-green shades. Similarly, the reaction can be carried out employing furfurylamine, fl-furylethylamine or 'y-furylpropylamine in place of fi-tetrahydrofurfurylamine.

Example 6 19 grams of 5,8-dihydroxy-lA-naphthoquinone and 1 gram of zinc dust are placed in 500 cc. of butanol to which has been added grams of tetrahydrofurfurylamine, 25 grams of aniline and 25 grams of cyclohexylamine. The mixture is heated on a water-bath at 60-70 C. until no further color change takes place and the reaction mixture is then worked up as described in Example 1. The reaction product obtained dyes cellulose acetate silk a dischargeable bluish-green shade.

Cyclohexylamine in the above example can be replaced, for example, by benzylamine, 0-, mand p-anisidine and an aminophenol to obtain dye compounds which similarly color cellulose acetate silk greenish-blue and which are included within the scope of our invention.

Example 7 19 grams of leuco 5,8-dihydroxy-l,4-naphthoquinone are reacted in butanol with 15 grams of tetrahydrofurfurylamine, 15 grams of 2-aminopyridine and 10 grams of ethanolamine. When reaction is complete, air is passed into the reaction mixture to oxidize the leuco dye formed to the non-leuco form following which the reaction product is worked up as described in Example 1. Cellulose acetate silk is dyed a bluishgreen shade by the dye product of this example.

Morpholine, 2-aminothiophene, 3-amino furan and aminocarbazole, for example, can be substituted for the Z-aminopyridine of the example to obtain dye compounds which color cellulose acetate silk bluish-green shades and which are included within the scope of our invention.

Example 8 19 grams of 5,8-dihydroxy-1,4-naphthoquinone, grams of a 40% aqueous solution composed of equal molecular parts of sodium taurinate, tetrahydrofurfurylamine and laurylamine are reacted as described in Example 1. The dye compound formed by this reaction is salted out by the addition of sodium chloride, recovered by filtration, washed with water and dried. The reaction product obtained is water soluble and dyes cellulose acetate silk a bluish-green shade.

In place of sodium taurinate, the sodium salt of another alkylamino sulfonate can be employed to obtain dye compounds which color cellulose acetate silk bluish-green shades. Similarly, glycine may be so employed to obtain a dye compound which likewise dyes cellulose acetate silk a bluish-green shade.

Example 9 It will be understood that the foregoing exv amples are intended to be illustrative and not limitative of our invention since many other compounds included within the scope of our invention can be prepared. Additional amine mixtures which can be reacted with 5,8-dihydroxylA-naphthoquinone in accordance with the methods described herein to obtain dye compounds of our invention include, for example, furfurylamine and cyclohexylamine, -furylpropylamine, methylamine and ethanolamine, e-furylethylamine and ,B-chloroethylamine, B- tetrahydrofurfurylethylamine, ,B-methoxyethylamine and ,o-hydroxypropylamine and fi-fi-hydroxyethyltetrahydrofurfurylamine and ethylamine.

The substituted 1,4-naphthoquinone dye compounds of our invention are, for the most part, relatively insoluble in water. Those compounds which are insoluble in water may be advantageously employed for the direct dyeing of organic derivative of cellulose textile materials by grinding the dye to a fine powder, intimately mixing it with a suitable dispersing or solubilizing agent and adding the resulting mixture to water or a dilute solution of soap in water to form an aqueous dyebath. Following this known preparation of the dyebath, the textile material or materials to be dyed may be added to the dyebath and the dyeing operation conducted in known fashion. The dye compounds of our invention which are water soluble do not, of course, require the use of a dispersing or solubili'zing agent but may be applied to organic derivatives of cellulose textile materials from an aqueous solution of the dye to our U. S. Letters 4- which may contain salt. For a more complete description. as to how the water insoluble dye compounds of our invention may be employed in coloring operations, reference may be had to our U. S. Letters Patent No. 2,115,030; issued April 26, 1938. For a more detailed description as to how the water soluble dye compounds of our invention may be employed, reference may be had Patent No. 2,107,898. issued February 8, 1938. The sulfonated dye compounds of our invention can be employed for the dyeing of wool and silk in accordance with methods known in the art for the coloration of these materials.

lA-naphthoquinone compounds containing two different alkylamino groups are shown in Examples 4 and 5, for example. Compounds of this character are more particularly described and claimed in our copending application Serial No. 308,458, filed of even date herewith.

We claim:

1. A lA-naphthoquinone compound having the general formula:

wherein X represents a iuran amino radical and Y and Z each represents a member selected from the group consisting of a hydroxy group, a furan-, an alkyl-, a cycloalky1-, an allyl-, an aralkyl-, an aryland a heterocyclic-amino group.

2. The 1,4-naphthoquinone compound having the formula:

no 0 3. The 1,4-naphthoquinone compound having the formula:

4. The 1,4-naphthoquinone compound having the formula:

H HOCHzCHr-I? (d 5. An organic derivative of cellulose textile material colored with a nuclear unsulfonated naphthazarine compound having the general formula:

wherein X represents a furan amino radical and Y and Z each represents a member selected from the group consisting of a hydroxy group, a furan-, an alkyl-, a cycloalkyl, an.allyl-, an aralkyl-, an aryland a heterocyclic-amiho group.

6. A cellulose acetate colored with a nuclear unsulfonated lA-naphthoquinone compound having the general formula:

wherein Z and Y each represents a member selected from the group consisting of a hydroxy group, a furanamino group, an alkylamino group, a cycloalkylamino group, an aralkylamino group, an arylamino group and a heterocyclicamino group.

' JOSEPH B. DICKEY. JAMES G. MCNALLY.

an allylamino group,

- CERTIFICATE OF CORRECTION. Patent No. 2,275,7h1. March 10, 19h2.

JOSEPH B. DICKEY, ET AL.

It is hereb y certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, first column, line 22, for "naphthazarine" read --5,8-dihj7droxy-l,l -naphthoquinon and'ihat the said Letters Patent should be read with this correction therein 'thet the same may conform to the record of the case in the Patent Office.

Signed and sealed this 26th day of May, A. D. 19h2.

- Henry Van Arsdale, (Seal) Acting Commissioner of -Pate nts. 

